The present invention relates to polycarbonate moulding compositions incorporating phosphonate amines, which are flame resistant and have a good level of mechanical properties, especially a high heat resistance, and are low-juicing.
U.S. Pat. Nos. 4,073,767 and 5,844,028 describe cyclic phosphorus compounds, including phosphorinane rings, as suitable flame retardants for polyurethanes, polyesters, polycarbonates and polyamides. In U.S. Pat. No. 4,397,750, certain cyclic phosphonate esters are described as efficient flame retardants for polypropylene and other polyolefins. In U.S. Pat. Nos. 5,276,066 and 5,844,028 certain (1,3,2-dioxaphosphorinane methane)amines are described which can be used as flame retardants in polyurethanes, polyesters, styrene polymers, polyvinyl chloride, polyvinyl acetate or polycarbonate.
U.S. Pat. No. 3,505,431, French Patent 1 371 139, U.S. Pat. Nos. 3,711,577, 4,054,544 describe acyclic triphosphonate amines which are partly halogenated.
In EP-A 0 640 655, moulding compositions of aromatic polycarbonate, styrene-containing copolymers and graft polymers are described, which can be rendered flame resistant with monomeric and/or oligomeric phosphorus compounds.
In EP-A 0 363 608, flame-resistant polymer mixtures of aromatic polycarbonate, styrene-containing copolymer or graft copolymer and oligomeric phosphates as flame retardants are described. For some applications, such as for example moulded parts in the interior of housing parts, the heat resistance of these mixtures is often inadequate.
In U.S. Pat. No. 5,061,745 polymer mixtures of aromatic polycarbonate, ABS graft polymer and/or styrene-containing copolymer and monophosphates as flame retardants are described. The level of the stress cracking resistance of these mixtures is often inadequate for producing thin-walled housing parts.
The object of the present invention is therefore to provide flame-resistant PC moulding compositions which have excellent heat resistance, good mechanical properties and low volatility of the phosphorus components in the moulding composition (low-juicing).
Surprisingly, it has now been found that, by using the phosphonate amines according to the invention, flame-resistant moulding compositions are obtained which give mouldings with a very good level of mechanical properties and outstanding heat resistance.
The invention therefore provides compositions containing polycarbonate and 0.1 to 30 parts by weight, preferably 1 to 25 parts by weight, particularly preferably 2 to 20 parts by weight, phosphonate amine of formula (I)
A3xe2x88x92yxe2x80x94Nxe2x80x94Byxe2x80x83xe2x80x83(I),
in which
A denotes a group of the formula (IIa) 
or (IIb) 
R1 and R2, independently of one another, denote unsubstituted or substituted C1-C10 alkyl or unsubstituted or substituted C6-C10 aryl,
R3 and R4, independently of one another, denote unsubstituted or substituted C1-C10 alkyl or unsubstituted or substituted C6-C10 aryl, or
R3 and R4 together denote unsubstituted or substituted C3-C10 alkylene,
y signifies the numerical values 0, 1 or 2 and
B independently denotes hydrogen, optionally halogenated C2-C8 alkyl, unsubstituted or substituted C6-C10 aryl.
The present invention preferably provides flame-resistant blends containing
A) 5 to 95, preferably 10 to 90 parts by weight, particularly preferably 20 to 80 parts by weight, aromatic polycarbonate and/or polyester carbonate
B) 1 to 60, preferably 1 to 40 parts by weight, particularly preferably 2 to 30 parts by weight, of at least one graft polymer of
B.1 5 to 95, preferably 20 to 60 wt. % one or more vinyl monomers on
B.2 5 to 95, preferably 40 to 80 wt. % one or more polymer backbones with a glass transition temperature of  less than 10xc2x0 C., preferably 0xc2x0 C., particularly preferably  less than xe2x88x9220xc2x0 C. and an average particle size (d50 value) of 0.05 to 5 xcexcm, preferably 0.20 to 0.35 xcexcm, particularly preferably 0.25 to 0.30 xcexcm,
C) 0 to 50, preferably 1 to 30, particularly preferably 2 to 25, parts by weight thermoplastic vinyl (co)polymer and/or polyalkylene terephthalate,
D) 0.1 to 30 parts by weight, preferably 1 to 25 parts by weight, particularly preferably 2 to 20 parts by weight, phosphonate amine of formula (I)
A3xe2x88x92yxe2x80x94Nxe2x80x94Byxe2x80x83xe2x80x83(I),
in which
A, B and y have the meaning given above and
E) 0 to 5 parts by weight, preferably 0.1 to 1 part by weight, particularly preferably 0.1 to 0.5 parts by weight, fluorinated polyolefin,
the sum of the parts by weight of all the components A+B+C+D+E making 100.
Component A
Aromatic polycarbonates and/or aromatic polyester carbonates as in component A which are suitable according to the invention are known from the literature or can be prepared by methods known from the literature (for the preparation of aromatic polycarbonates see for example Schnell, xe2x80x9cChemistry and Physics of Polycarbonatesxe2x80x9d, Interscience Publishers, 1964, and DE-AS 1 495 626, DE-OS 2 232 877, DE-OS 2 703 376, DE-OS 2 714 544, DE-OS 3 000 610, DE-OS 3 832 396; for the preparation of aromatic polyester carbonates e.g. DE-OS 3 077 934).
Aromatic polycarbonates are prepared e.g. by reacting diphenols with carbonic acid halides, preferably phosgene and/or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, by the phase boundary process, optionally using chain terminators, for example monophenols, and optionally using trifunctional or more than trifunctional branching agents, for example triphenols or tetraphenols.
Diphenols for the preparation of the aromatic polycarbonates and/or aromatic polyester carbonates are preferably those of formula (III) 
wherein
A1 is a single bond, C1-C5 alkylene, C2-C5 alkylidene, C5-C6 cycloalkylidene, xe2x80x94Oxe2x80x94, xe2x80x94SOxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SO2xe2x80x94, C6-C12 arylene, which can be condensed with other aromatic rings optionally containing heteroatoms, or a group of the formula 
or a group of the formula (V) 
B independently of one another, is C1-C8 alkyl, preferably C1-C4 alkyl especially methyl, halogen, preferably chlorine and/or bromine, C6-C10 aryl, preferably phenyl, C7-C12 aralkyl, phenyl C1-C4 alkyl, preferably benzyl,
x each independently of one another, is 0, 1 or 2,
p is 1 or 0 and
R5 and R6, selectable individually for each Z, independently of one another, signify hydrogen or C1-C6 alkyl, preferably hydrogen, methyl and/or ethyl,
Z signifies carbon and
m signifies an integer from 4 to 7, preferably 4 or 5,
with the proviso that, on at least one atom Z,
R5 and R6 are both alkyl.
Preferred diphenols are hydroquinone, resorcinol, 4,4xe2x80x2-dihydroxydiphenyl, bis(hydroxyphenyl) C1-C5 alkanes, bis(hydroxyphenyl) C5-C6 cycloalkanes, bis(hydroxyphenyl)ethers, bis(hydroxyphenyl) sulfoxides, bis(hydroxyphenyl) ketones, bis(hydroxyphenyl) sulfones and xcex1,xcex1-bis(hydroxyphenyl) diisopropylbenzenes and the ring-brominated and/or ring-chlorinated derivatives thereof.
Particularly preferred diphenols are 4,4xe2x80x2-diphenylphenol, bisphenol A, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4xe2x80x2-dihydroxydiphenyl sulfide, 4,4xe2x80x2-dihydroxydiphenyl sulfone and the di- and tetrabrominated or chlorinated derivatives thereof such as, for example, 2,2-bis(3-chloro -4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane or 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane.
2,2-Bis(4-hydroxyphenyl)propane (bisphenol A) is particularly preferred.
The diphenols can be used individually or as any mixtures.
The diphenols are known from the literature or are obtainable by methods known from the literature.
Suitable chain terminators for the preparation of the thermoplastic, aromatic polycarbonates are, for example, phenol, p-chlorophenol p-tert.-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols, such as 4-(1,3-tetramethylbutyl)phenol according to DE-OS 2 842 005 or monoalkylphenol or dialkylphenols with a total of 8 to 20 C atoms in the alkyl substituents, such as 3,5-di-tert.-butylphenol, p-isooctylphenol, p-tert-octylphenol, p-dodecylphenol and 2-(3,5-dimethylheptyl)phenol and 4-(3,5-dimethylheptyl)phenol. The quantity of chain terminators to be used is generally between 0.5 mole % and 10 mole %, based on the sum of moles of the diphenols used in each case.
The thermoplastic, aromatic polycarbonates have average weight average molecular weights (Mw, measured e.g. by ultracentrifuge or nephelometry) of 10 000 to 200 000, preferably 20 000 to 80 000.
The thermoplastic, aromatic polycarbonates can be branched by known means, preferably by incorporating 0.05 to 2.0 mole %, based on the sum of the diphenols used, ofxe2x89xa7trifunctional compounds, e.g. those withxe2x89xa7three phenolic groups.
Both homopolycarbonates and copolycarbonates are suitable. To prepare copolycarbonates according to the invention as component A, it is also possible to use 1 to 25 wt. %, preferably 2.5 to 25 wt. % (based on the total quantity of diphenols to be used), polydiorganosiloxanes with hydroxy-aryloxy end groups. These are known (cf. for example U.S. Pat. No. 3,419,634) or can be prepared by methods known from the literature. The preparation of polydiorganosiloxane-containing copolycarbonates is described e.g. in DE-OS 3 334 782.
Preferred polycarbonates are, in addition to bisphenol A homopolycarbonates, the copolycarbonates of bisphenol A with up to 15 mole %, based on the sums of moles of diphenols, other diphenols mentioned as preferred or particularly preferred, especially 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane.
Aromatic dicarboxylic acid dihalides for the preparation of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4,4xe2x80x2-dicarboxylic acid and of 2,6-naphthalenedicarboxylic acid.
Mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in a ratio of between 1:20 and 20:1 are particularly preferred.
In the preparation of polyester carbonates, a carbonic acid halide, preferably phosgene, is additionally incorporated as a bifunctional acid derivative.
In addition to the monophenols already mentioned, their chloroformates and the acid chlorides of aromatic monocarboxylic acids which can optionally be substituted by C1-C22 alkyl groups or by halogen atoms, and aliphatic C2-C22 monocarboxylic acid chlorides, are also suitable as chain terminators for the preparation of the aromatic polyester carbonates.
The quantity of chain terminators is 0.1 to 10 mole % in each case, based on moles of diphenol in the case of phenolic chain terminators and on moles of dicarboxylic acid dichlorides in the case of monocarboxylic acid chloride chain terminators.
The aromatic polyester carbonates can also contain incorporated aromatic hydroxycarboxylic acids.
The aromatic polyester carbonates can be both linear and branched by a known method (cf. also DE-OS 2 940 024 and DE-OS 3 007 934).
Examples of branching agents which can be used are trifunctional or polyfunctional carboxylic acid chlorides, such as trimesic acid trichloride, cyanuric acid trichloride, 3,3xe2x80x2-4,4xe2x80x2-benzophenonetetracarboxylic acid tetrachloride, 1,4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in quantities of 0.01 to 1.0 mole % (based on dicarboxylic acid dichlorides used) or trifunctional or polyfunctional phenols, such as phloroglucinol, 4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)heptene-2, 4,4-dimethyl-2,4,6-tri(4-hydroxyphenyl)heptane, 1,3,5-tri(4-hydroxyphenyl)benzene, 1,1,1-tri(4-hydroxyphenyl)ethane, tri(4-hydroxyphenyl)phenylmethane, 2,2-bis[4,4-bis(4-hydroxyphenyl)cyclohexyl]propane, 2,4-bis(4-hydroxyphenylisopropyl)phenol, tetra(4-hydroxyphenyl)methane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)propane, tetra-(4-[4-hydroxyphenylisopropyl]phenoxy)methane, 1,4-bis[4,4xe2x80x2-dihydroxytriphenyl)methyl]benezene, in quantities of 0.01 to 1.0 mole %, based on diphenols used, Phenolic branching agents can be placed in the initial mixture with the diphenols; acid chloride branching agents can be added together with the acid dichlorides.
In the thermoplastic, aromatic polyester carbonates, the proportion of carbonate structural units can be varied at will.
The proportion of carbonate groups is preferably up to 100 mole %, especially up to 80 mole %, particularly preferably up to 50 mole %, based on the sum of ester groups and carbonate groups.
Both the ester portion and the carbonate portion of the aromatic polyester carbonates can be present in the form of blocks or randomly distributed in the polycondensate.
The relative solution viscosity (xcex7rel) of the aromatic polyester carbonates is in the range of 1.18 to 1.4, preferably 1.22 to 1.3 (measured on solutions of 0.5 g polyester carbonate in 100 ml methylene chloride solution at 25xc2x0 C.).
The thermoplastic, aromatic polycarbonates and polyester carbonates can be used alone or in any mixture with one another.
Component B
Component B according to the invention represents graft polymers. These comprise graft copolymers with rubber-elastic properties, which are substantially obtainable from at least 2 of the following monomers: chloroprene, 1,3-butadiene, isopropene, styrene, substituted styrenes, acrylonitrile, ethylene, propylene, vinyl acetate and (meth)acrylates with 1 to 18 C atoms in the alcohol component; i.e. polymers as described e.g. in xe2x80x9cMethoden der Organischen Chemiexe2x80x9d (Houben-Weyl), vol. 14/1, Georg Thieme-Verlag, Stuttgart 1961, p. 393-406 and in C. B. Bucknall, xe2x80x9cToughened Plasticsxe2x80x9d, Appl. Science Publishers, London 1977. Preferred polymers B are partially crosslinked and possess gel contents of more than 20 wt. %, preferably more than 40 wt. %, especially more than 60 wt. %.
Preferred graft polymers B comprise graft polymers of:
B.1 5 to 95, preferably 30 to 80 parts by weight of a mixture of
B.1.1 50 to 99 parts by weight styrene, xcex1-methylstyrene, styrenes substituted in the ring with halogen or methyl, methyl methacrylate or mixtures of these compounds and
B.1.2 1 to 50 parts by weight acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride, C1-C4 alkyl- or phenyl-N-substituted maleimides or mixtures of these compounds on
B.2 5 to 95, preferably 20 to 70 parts by weight polymer with a glass transition temperature of less than xe2x88x9210xc2x0 C., preferably based on diene and/or alkyl acrylate.
Particularly preferred as polymer backbone B.2 is polybutadiene with optionally up to 30 wt. % styrene or acrylonitrile as comonomer.
Preferred g polymers B are e.g. polymer backbones B.2 such as polybutadiene, butadiene/styrene copolymers and polyacrylate rubbers grafted with styrene and/or acrylonitrile and/or alkyl (meth)acrylates; i.e. copolymers of the type described in DE-OS 1 694 173 (=U.S. Pat. No. 3,564,077); polybutadienes, butadiene/styrene or butadiene/acrylonitrile copolymers, polyisobutenes or polyisoprenes grafted with alkyl acrylates or methacrylates, vinyl acetate, acrylonitrile, styrene and/or alkyl styrenes, as described e.g. in DE-OS 2 348 377 (=U.S. Pat. No. 3,919,353).
Particularly preferred polymers B are e.g. ABS polymers, as described e.g. in DE-OS 2 035 390 (=U.S. Pat. No. 3,644,574) or in DE-OS 2 248 242 (=GB-B 1 409 275).
Particularly preferred graft polymers B are obtainable by the grafting reaction of
xcex1 10 to 70, preferably 15 to 50, especially 20 to 40 wt. %, based on graft polymer B, of at least one (meth)acrylate or 10 to 70, preferably 15 to 50, especially 20 to 40 wt. % of a mixture of 10 to 50, preferably 20 to 35 wt. %, based on mixture, acrylonitrile or (meth)acrylate and 50 to 90, preferably 65 to 80 wt. %, based on mixture, styrene, as graft B.1 on
xcex2 30 to 90, preferably 50 to 85, especially 60 to 80 wt. %, based on graft polymer B, of a butadiene polymer with at least 50 wt. %, based on xcex2, of butadiene groups as polymer backbone B.2.
The gel content of the polymer backbone xcex2 is preferably at least 70 wt. % (measured in toluene), the degree of grafting G 0.15 to 0.55 and the average particle diameter d50 of the graft polymer B.2 0.05 to 2 xcexcm, preferably 0.1 to 0.6 xcexcm.
(Meth)acrylates xcex1 are esters of acrylic acid or methacrylic acid with monohydric alcohols with 1 to 18 C atoms. Particularly preferred are methyl methacrylate, ethyl methacrylate and propyl methacrylate, n-butyl acrylate, t-butyl acrylate and t-butyl methacrylate.
In addition to butadiene groups, the polymer backbone xcex2 can contain up to 50 wt. %, based on xcex2, groups of other ethylenically unsaturated monomers, such as styrene, acrylonitrile, esters of acrylic or methacrylic acid with 1 to 4 C atoms in the alcohol component (such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate), vinyl esters and/or vinyl ethers. The preferred polymer backbone xcex2 consists of pure polybutadiene.
The degree of grafting G refers to the weight ratio of grafting monomers grafted on to the polymer backbone and is dimensionless.
The average particle size d50 is the diameter above and below which 50 wt. % of the particles respectively lie. It can be determined by means of ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. und Z. Polymere 250 (1972), 782-796).
Particularly preferred polymers B are e.g. also graft polymers of
xcfx84. 20 to 90 wt. %, based on component B, polyacrylate rubber with a glass transition temperature of less than xe2x88x9220xc2x0 C. as polymer backbone B.2 and
xcex4 10 to 80 wt. %, based on component B, of at least one polymerisable, ethylenically unsaturated monomer as graft monomers C.1.
The polyacrylate rubbers xcfx84 of polymers B are preferably polymers of alkyl acrylates, optionally with up to 40 wt. %, based on xcfx84, of other polymerisable, ethylenically unsaturated monomers. The preferred polymerisable acrylates include C1-C8 alkyl esters, e.g. methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; halogen alkyl esters, preferably halogen C1-C8 alkyl esters such as chloroethyl acrylate, and mixtures of these monomers.
Monomers with more than one polymerisable double bond can be copolymerised for the purpose of crosslinking. Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 C atoms and unsaturated monohydric alcohols with 3 to 12 C atoms or saturated polyols with 2 to 4 OH groups and 2 to 20 C atoms, such as e.g. ethylene glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, such as e.g. trivinyl and triallyl cyanurate; polyfunctional vinyl compounds, such as di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.
Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethy acrylate, diallyl phthalate and heterocyclic compounds having at least 3 ethylenically unsaturated groups.
Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, trivinyl cyanurate, triacryloylhexahydro-s-triazine, triallyl benzenes.
The quantity of the crosslinking monomers is preferably 0.02 to 5, especially 0.05 to 2 wt. %, based on the polymer backbone xcfx84.
When using cyclic crosslinking monomers with at least 3 ethylenically unsaturated groups, it is advantageous to limit the quantity to less than 1 wt. % of the polymer backbone xcfx84.
Preferred xe2x80x9cotherxe2x80x9d polymerisable, ethylenically unsaturated monomers that can optionally be used for the preparation of the polymer backbone xcfx84 in addition to the acrylates are e.g. acrylonitrile, styrene, xcex1-methylstyrene, acrylamide, vinyl C1-C6 alkyl ether, methyl methacrylate, butadiene. Preferred polyacrylate rubbers as polymer backbone xcfx84 are emulsion polymers having a gel content of at least 60 wt. %.
Other suitable polymer backbones according to B.2 are silicone rubbers with graft-active points as described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE-OS 3 631 539.
The gel content of the polymer backbone B.2 is determined at 25xc2x0 C. in dimethylformamide (M. Hoffmann, H. Krxc3x6mer, R. Kuhn, Polymeranalytik I and II, Georg Thieme-Verlag, Stuttgart 1977).
The graft polymers B can be prepared by known processes such as bulk, suspension, emulsion or bulk suspension processes.
Since it is known that, during the grafting reaction, the grafting monomers are not necessarily completely grafted on to the polymer backbone, graft polymers B according to the invention are also understood to be those products obtained by polymerisation of the graft monomers in the presence of the polymer backbone.
The average particle size d50 is the diameter above and below which 50 wt. % of the particles respectively lie. It can be determined by means of ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. und Z. Polymere 250 (1972), 782-796).
Since it is known that, during the grafting reaction, the grafting monomers are not necessarily completely grafted on to the polymer backbone, graft polymers B according to the invention are also understood to be those products obtained by (co)polymerisation of the graft monomers in the presence of the polymer backbone and formed during working up.
Component C
Component C comprises one or more thermoplastic vinyl (co)polymers C.1, polyalkylene terephthalates C.2 or mixtures thereof.
Suitable as (co)polymers C.1 are polymers of at least one monomer from the group of vinyl aromatics, vinyl cyanides, such as unsaturated nitrites, C1-C8 alkyl (meth)acrylates, unsaturated carboxylic acids and derivatives such as anhydrides and imides of unsaturated carboxylic acids.
Especially suitable are (co)polymers of
C.1.1 50 to 99 parts by weight of vinyl aromatics and/or ring-substituted vinyl aromatics, such as e.g. styrene, xcex1-methylstyrene, p-methylstyrene, p-chlorostyrene, and/or C1-C4 alkyl methacrylates such as e.g. methyl methacrylate, ethyl methacrylate, and
C.1.2 1 to 50 parts by weight of vinyl cyanides such as unsaturated nitrites, e.g. acrylonitrile and methacrylonitrile and/or C1-C8 alkyl (meth)acrylates, e.g. methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and/or unsaturated carboxylic acids such as maleic acid and/or derivatives, such as anhydrides and imides of unsaturated carboxylic acids, such as e.g. maleic anhydride and N-phenylmaleimide.
The (co)polymers C.1 are resinous, thermoplastic and rubber-free.
Copolymers of C.1.1 styrene and C.1.2 acrylonitrile are particularly preferred.
The (co)polymers according to C.1 are known and can be prepared by radical polymerisation, especially by emulsion, suspension, solution or bulk polymerisation. The (co)polymers according to component C preferably possess molecular weights Mw (weight average, determined by light scattering or sedimentation) of between 15 000 and 200 000.
The polyalkylene terephthalates of component C.2 are reaction products of aromatic dicarboxylic acids or their reactive derivatives, such as dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products.
Preferred polyalkylene terephthalates contain at least 80 wt. %, preferably at least 90 wt. %, based on the dicarboxylic acid component, terephthalic acid groups and at least 80 wt. %, preferably at least 90 mole %, based on the diol component, ethylene glycol and/or 1,4-butanediol groups.
In addition to terephthalic acid esters, the preferred polyalkylene terephthalates can contain up to 20 mole %, preferably up to 10 mole %, groups of other aromatic or cycloaliphatic dicarboxylic acids with 8 to 14 C atoms or aliphatic dicarboxylic acids with 4 to 12 C atoms, such as e.g. groups of phthalic acid, isophthalic acid, 2,6-naphthalenedicarboyxlic acid, 4,4xe2x80x2-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid.
In addition to ethylene glycol or 1,4-butanediol groups, the preferred polyalkylene terphthalates can contain up to 20 mole %, preferably up to 10 mole %, other aliphatic diols with 3 to 12 C atoms or cycloaliphatic diols with 6 to 21 C atoms, e.g. groups of 1,3-propanediol, 2-ethyl-1,3-propanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 3-ethyl-2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,2-diethyl-1,3-propanediol, 2,5-hexanediol, 1,4-di(xcex2-hydroxyethoxy)benzene, 2,2-bis(4-hydroxycyclohexyl)propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis(4-xcex2-hydroxyethoxyphenyl)propane and 2,2-bis(4-hydroxypropoxyphenyl)propane (DE-OS 2 407 674, 2 407 776, 2 715 932).
The polyalkylene terephthalates can be branched by incorporating relatively small quantities of 3- or 4-hydric alcohols or 3- or 4-basic carboxylic acids, e.g. according to DE-OS 1 900 270 and U.S. Pat. No. 3,692,744. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol.
Particularly preferred are polyalkylene terephthalates which have been prepared solely from terephthalic acid and the reactive derivatives thereof (e.g. its dialkyl esters) and ethylene glycol and/or 1,4-butanediol, and mixtures of these polyalkylene terephthalates.
Mixtures of polyalkylene terephthalates contain 1 to 50 wt. %, preferably 1 to 30 wt. %, polyethylene terephthalate and 50 to 99 wt. %, preferably 70 to. 99 wt. %, polybutylene terephthalate.
The polyalkylene terephthalates preferably used generally possess an intrinsic viscosity of 0.4 to 1.5 dl/g, preferably 0.5 to 1.2 dl/g, measured in phenol/o-dichlorobenzene (1:1 parts by weight) at 25xc2x0 C. in an Ubbelohde viscometer.
The polyalkylene terephthalates can be prepared by known methods (cf. e.g. Kunststoff-Handbuch, vol. VIII, p. 695 et seq., Carl-Hanser-Verlag, Munich 1973).
Component D
The moulding compositions according to the invention contain as flame retardants at least one phosphonate amine of formula (I)
A3xe2x88x92yxe2x80x94Nxe2x80x94Byxe2x80x83xe2x80x83(I),
in which 
A denotes
wherein
R1, R2, R3 and R4 and also B and y have the meaning given above.
B preferably denotes, independently, hydrogen, ethyl, n- or iso-propyl, which can be substituted by halogen, unsubstituted C6-C10 aryl or C6-C10 aryl substituted by C1-C4 alkyl and/or halogen, especially phenyl or naphthyl.
Alkyl in R1, R2, R3 and R4 independently denotes preferably methyl ethyl, n-propyl, iso-propyl, n-, iso-, sec.- or tert.-butyl, pentyl or hexyl.
Substituted alkyl in R1, R2, R3 and R4 independently denotes preferably halogen-substituted C1-C10 alkyl, especially mono- or disubstituted methyl ethyl, n-propyl, iso-propyl, n-, iso-, sec.- or tert.-butyl, pentyl or hexyl.
R3 and R4, together with the carbon to which they are bonded, preferably form cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, especially cyclopentyl or cyclohexyl.
In R1, R2, R3 and R4, C6-C10 aryl independently denotes preferably phenyl, naphthyl or binaphthyl, especially o-phenyl, o-naphthyl, o-binaphthyl, which can be substituted (generally mono-, di- or trisubstituted) by halogen.
The following are mentioned as preferable and by way of examples: 5,5,5xe2x80x25xe2x80x2,5xe2x80x3,5xe2x80x3-hexamethyltris(1,3,2-dioxaphosphorinanemethane)amin-2,2xe2x80x2,2xe2x80x3-trioxide of formula (I-1) 
(experimental product XPM 1000 from Solutia Inc., St. Louis, USA) 1,3,2-dioxaphosphorinane-2-methanamine, N-butyl-N[(5,5-dimethyl-1,3,2-dioxaphosphorinan-2-yl)methyl]-5,5-dimethyl-, P,2-dioxides; 1,3,2-dioxaphosphorinane-2-methanamine, N-[(5,5-dimethyl-1,3,2-dioxaphosphorinan-2-yl)methyl]-5,5-dimethyl-N-phenyl-, P,2-dioxide; 1,3,2-dioxaphosphorinane-2-methanamine, N,N-dibutyl-5,5-dimethyl-, 2-oxide, 1,3,2-dioxaphosphorinane-2-methanamine, N-[(5,5-dimethyl-1,3,2-dioxaphosphorinan-2-yl)methyl]-N-ethyl-5,5-dimethyl-, P,2-dioxide, 1,3,2-dioxaphosphorinane-2-methanamine, N-butyl-N-[(5,5-dichloromethyl-1,3,2-dioxaphosphorinan-2-yl)methyl]-5,5-dichloromethyl-, P,2-dioxide, 1,3,2-dioxaphosphorinane-2-methanamine, N-[(5,5-dichloromethyl-1,3,2-dioxaphosphorinan-2-yl)methyl]-5,5-dichloromethyl-N-phenyl, P,2-dioxide; 1,3,2-dioxaphosphorinane-2-methanamine, N,N-di-(4-chlorobutyl)-5,5-dimethyl-2-oxides; 1,3,2-dioxaphosphorinane-2-methanimine, N-[(5,5-dimethyl-1,3,2-dioxaphosphorinan-2-yl)methane]-N-(2-chloroethyl)-5,5-di(chloromethyl)-, P2-dioxide.
The following are also preferred:
Compounds of formulae (I-2) or (I-3) 
wherein
R1, R2, R3 and R4 have the meanings given above.
Compounds of formulae (I-2), (I-1) are particularly preferred. The individual compounds mentioned above are also particularly preferred.
The compounds of formula (I) can be prepared by the following methods:
a) PCl3 is added to a mixture of 1,3-diol derivatives, water and an organic solvent at a temperature of 10-60xc2x0 C. A 5,5-substituted 1,3,2-dioxaphosphorinane-2-oxide of formula (Ia) 
is obtained, wherein R1 and R2 have the meaning given above,
b) after purification, the 1,3,2-dioxaphosphorinane-2-oxide is reacted in para-formaldehyde with an amine ByNH3xe2x88x92y, wherein B and y have the meaning given above,
c) after purifying again and drying, the phosphonate amine of formula (I) is obtained.
A detailed description of the preparation method can be taken from U.S. Pat. No. 5,844,028.
Component E
The fluorinated polyolefins E are of high molecular weight and possess glass transition temperatures of more than xe2x88x9230xc2x0 C., generally more than 100xc2x0 C., fluorine contents, preferably of 65 to 76, especially of 70 to 76 wt. %, average particle diameters d50 of 0.05 to 1 000, preferably 0.08 to 20 xcexcm. The fluorinated polyolefins E generally have a density of 1.2 to 2.3 g/cm3. Preferred fluorinated polyolefins E are polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene (hexafluoropropylene and ethylene/tetrafluoroethylene copolymers. The fluorinated polyolefins are known (cf. xe2x80x9cVinyl and Related Polymersxe2x80x9d by Schildknecht, John Wiley and Sons, Inc., New York, 1962, pages 484-494; xe2x80x9cFluorpolymersxe2x80x9d by Wall, Wiley-Interscience, John Wiley and Sons, Inc., New York, volume 13, 1970, pages 623-654; xe2x80x9cModem Plastics Encyclopediaxe2x80x9d, 1970-1971, volume 47, part 10 A, October 1970, McGraw-Hill Inc., New York, pages 134 and 774; xe2x80x9cModern Plastics Encyclopediaxe2x80x9d, 1975-1976, October 1975, volume 52, part 10 A, McGraw-Hill Inc., New York, pages 27, 28 and 472 and U.S. Pat. Nos. 3,671,487, 3,723,373 and 3,838,092).
They can be prepared by known methods, for example by polymerisation of tetrafluoroethylene in an aqueous medium with a free radical-forming catalyst, e.g. sodium, potassium or ammonium peroxydisulfate at pressures of 7 to 71 kg/cm2 and at temperatures of 0 to 200xc2x0 C., preferably at temperatures of 20 to 100xc2x0 C. (For further details, cf. e.g. U.S. Pat. No. 2,393,967). Depending on the form in which they are used, the density of these materials can be between 1.2 and 2.3 g/cm3, and the average particle size between 0.5 and 1 000 xcexcm.
Preferred fluorinated polyolefins E according to the invention are tetrafluoroethylene polymers with average particle diameters of 0.05 to 20 xcexcm, preferably 0.08 to 10 xcexcm, and a density of 1.2 to 1.9 g/cm3, and are preferably used in the form of a coagulated mixture of emulsions of the tetrafluoroethylene polymers E with emulsions of the graft polymers B.
Suitable fluorinated polyolefins E which can be used in powdered form are tetrafluoroethylene polymers with average particle diameters of 100 to 1 000 xcexcm and densities of 2.0 g/cm3 to 2.3 g/cm3.
Other preferred preparations are the fluorinated polyolefins E:
E.1) as a coagulated mixture with at least one of components A to C, the fluorinated polyolefin E or polyolefin mixture in the form of an emulsion being mixed with at least one emulsion of components A to C and then coagulated
or
E.2) as a precompound with at least one of components A to C, the fluorinated polyolefins E in the form of a powder being blended with a powder or granules of at least one of components A to C and compounded in the melt, generally at temperatures of 208xc2x0 C. to 330xc2x0 C. in the conventional equipment such as internal mixers, extruders or double-shaft screws.
Preferred preparations for the fluorinated polyolefins E are coagulated mixtures with a graft polymer B or a vinyl (co)polymer C.1.
To prepare a coagulated mixture of B and E, an aqueous emulsion (latex) of a graft polymer B is first blended with a fine-particle emulsion of a fluorinated polyolefin E; suitable emulsions of fluorinated polyolefins usually possess solids contents of 30 to 70 wt. %, especially 50 to 60 wt. %, preferably 30 to 35 wt. %.
The quantity stated in the description of components A, B and C does not contain the proportion of the graft polymer, vinyl (co)polymer or polycarbonate for the coagulated mixture according to E.1) and E.2).
The equilibrium ratio of graft polymer B or (co)polymers to the fluorinated polyolefin E in the emulsion mixture is 95:5 to 60:40, preferably 90:10 to 50:50. The emulsion mixture is then coagulated by known means, e.g. by spray drying, freeze drying or coagulation by means of adding inorganic or organic salts, acids, bases or organic, water-miscible solvents, such as alcohols, ketones, preferably at temperatures of 20 to 150xc2x0 C., especially 50 to 100xc2x0 C. If necessary, drying may be carried out at 50 to 200xc2x0 C., preferably 70 to 100xc2x0 C.
Suitable tetrafluoroethylene polymer emulsions are commercial products and are available for example from DuPont as Teflon 30 N.
The moulding compositions according to the invention can contain at least one of the conventional additives, such as lubricants and mould release agents, nucleating agents, antistatic agents, stabilisers and dyes, pigments and/or reinforcing material. Suitable inorganic reinforcing materials are glass fibres, optionally cut or ground, glass beads, glass spheres, lamellar reinforcing material such as kaolin, talc, mica, carbon fibres. Cut or ground glass fibres, preferably with a length of 1 to 10 mm and a diameter of  less than 20 xcexcm are preferably used as reinforcing material in a quantity of 1 to 40 parts by weight; the glass fibres are preferably surface-treated.
In addition, the moulding compositions according to the invention can contain at least one polar compound of at least one of the metals of main groups 1 to 5 or of subgroups 1 to 8 of the periodic table with at least one element selected from the group of oxygen, sulfur, boron, carbon, phosphorus, nitrogen, hydrogen and silicon as an extremely finely divided inorganic powder. An oxide or hydroxide, preferably TiO2, SiO2, SnO2, ZnO, boehmite, ZrO2, Al2O3, iron oxides, m thereof and doped compounds are preferably used as the polar compound, particularly preferably boehmite or TiO2, with an average particle diameter of  less than 200 nm, preferably 0.1-100 nm, particularly preferably 1-50 nm.
The moulding compositions according to the invention can contain one or more additional flame retardants, optionally having a synergistic action. Organic halogen compounds such as decabromobisphenyl ether, tetrabromobisphenol, inorganic halogen compounds such as ammonium bromide, nitrogen compounds such as melamine, melamine-formaldehyde resins, inorganic hydroxide compounds such as Mg, Al hydroxide, inorganic compounds such as antimony oxides, barium metaborate, hydroxoantimonate, zirconium oxide, zirconium hydroxide, molybdenum oxide, ammonium molybdate, zinc borate, ammonium borate and tin oxide and also siloxane compounds are mentioned as examples of other flame retardants. These flame retardants are generally added in a quantity of up to 20 wt. % (based on the total moulding composition).
In addition, phosphorus compounds of formula (VI) 
in which
R7, R8 and R9, independently of one another, are an optionally halogenated C1-C8 alkyl or an optionally halogenated and/or alkylated C5-C6 cycloalkyl or an optionally halogenated and/or alkylated and/or aralkylated C6-C30 aryl, and
xe2x80x9cnxe2x80x9d and xe2x80x9clxe2x80x9d, independently of one another, are 0 or 1,
are suitable as flame retardants
These phosphorus compounds are generally known (cf. e.g. Ullmann, Enzyklopxc3xa4die der technischen Chemie, vol. 18, pages 301 et seq., 1979 and EP-A 345 522. The aralkyated phosphorus compounds are described e.g. in DE-OS 38 24 356.
Optionally halogenated C1-C8 alkyl groups according to (VI) can be mono- or polyhalogenated, linear or branched Examples of alkyl groups are chloroethyl, 2-chloropropyl, 2,3-dibromopropyl, butyl methyl or octyl.
Optionally halogenated and/or alkylated C5-C6 cycloalkyls according to (VI) are optionally mono- to polyhalogenated and/or alkylated C5 or C6 cycloalkyls, i.e. e.g. cyclopentyl, cyclohexyl, 3,3,5-trimethylcyclohexyl and completely chlorinated cyclohexyl.
Optionally halogenated and/or alkylated and/or aralkylated C6-C30 aryl groups according to (VI) are optionally mono- or polynuclear, mono- or polyhalogenated and/or alkylated and/or aralkylated, e.g. chlorophenyl, bromophenyl, pentachlorophenyl, pentabromophenyl, phenyl, cresyl, isopropylphenyl, benzyl-substituted phenyl and naphthyl.
R7, R8 and R9 preferably denote, independently of one another, methyl, ethyl, butyl, octyl, phenyl, cresyl, cumyl or naphthyl. R5, R6 and R7 particularly preferably denote, independently of one another, methyl, ethyl, butyl, phenyl optionally substituted by methyl and/or ethyl.
Phosphorus compounds according to formula (VI) which can be used according to the invention are e.g. tributyl phosphate, tris(2-chloroethyl)phosphate, tris(2,3-dibromopropyl)phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, diphenyl-2-ethyl cresyl phosphate, tri(isopropyl phenyl)phosphate, tris(p-benzyl phenyl)phosphate, triphenylphosphine oxide, dimethyl methanephosphonate, dipentyl methanephosphonate and diethyl phenylphosphonate.
Dimeric and oligomeric phosphates, as described e.g. in EP-A 0 363 608, are also suitable flame retardants.
The moulding compositions according to the invention can contain phosphorus compounds according to formula (VII) 
as flame retardants.
In the formula, R10, R11, R12 and R13, independently of one another, denote C1-C8 alkyl C5-C6 cycloalkyl, C6-C20 aryl or C7-C12 aralkyl, optionally halogenated in each case.
R10, R11, R12 and R13 preferably denote, independently of one another, C1-C4 alkyl, phenyl, naphthyl or phenyl-C1-C4 alkyl. For their part the aromatic groups R10, R11, R12 and R13 can be substituted with halogen and/or alkyl groups, preferably chlorine, bromine and/or C1-C4 alkyl. Particularly preferred aryl groups are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl and the corresponding brominated and chlorinated derivatives thereof.
X in formula (VII) signifies a mono- or polynuclear aromatic group with 6 to 30 C atoms. This is preferably derived from diphenols of formula (III). Diphenylphenol, bisphenol A, resorcinol or hydroquinone or the chlorinated or brominated derivatives thereof are particularly preferred.
n in formula (VII) can be 0 or 1, independently of one another, n preferably being equal to 1.
k denotes values from 0 to 30, preferably an average value of 0.3 to 20, particularly preferably 0.5 to 10, especially 0.5 to 6.
Mixtures of 10 to 90 wt. %, preferably 12 to 40 wt. %, of at least one monophosphorus compound of formula (VI) and at least one oligomeric phosphorus compound, or a mixture of oligomeric phosphorus compounds as described in EP-A 363 608 and phosphorus compounds according to formula (VII) can also be used in quantities of 10 to 90 wt. %, preferably 60 to 88 wt. %, based on the total quantity of phosphorus compounds.
Monophosphorus compounds of formula (VI) are especially tributyl phosphate, tris(2-chloroethyl)phosphate, tris(2,3-dibromopropyl)phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, diphenyl-2-ethyl cresyl phosphate, tri(isopropyl phenyl)phosphate, halogen-substituted aryl phosphates, dimethyl methylphosphonate, diphenyl methylphosphonate, diethyl phenylphosphonate, triphenylphosphine oxide or tricresylphosphine oxide.
The mixtures of monomeric and oligomeric phosphorus compounds of formula (VII) have average k values of 0.3 to 20, preferably 0.5 to 10, especially 0.5 to 6.
The phosphorus compounds mentioned are known (cf. e.g. EP-A 363 608, EP-A 640 655) or can be prepared by known methods in an analogous fashion (e.g. Ullmanns Encyklopxc3xa4die der technischen Chemie, vol. 18, p. 301 et seq., 1979; Houben-Weyl, Methoden der organischen Chemie, vol. 12/1, p. 43; Beilstein vol. 6, p. 177).
The moulding compositions according to the invention containing the components A to E and optionally other known additives such as stabilisers, dyes, pigments, lubricants and mould release agents, nucleating agents, nanoparticles and also antistatic agents and reinforcing materials and flame retardants, are prepared in that the respective components are blended by known means and melt-compounded and melt-extruded at temperatures of 200xc2x0 C. to 300xc2x0 C. in conventional equipment such as internal mixers, extruders and double-shaft screws, component E preferably being used in the form of the coagulated mixture already mentioned.
The individual components can be blended by known means both successively and simultaneously, both at about 20xc2x0 C. (ambient temperature) and at elevated temperature.
The moulding compositions of the present invention can be used for the production of mouldings of all types. In particular, mouldings can be produced by injection moulding. Examples of mouldings which can be produced are: housing parts of all types, e.g. for domestic appliances such as juice presses, coffee machines, mixers, for office machinery such as monitors, printers, copiers or covers for the building sector and parts for the automotive sector. They are also used in the electrical engineering sector because they have very good electrical properties.
The moulding compositions according to the invention can also be used for example to produce the following mouldings or moulded parts:
parts for internal fittings in rail vehicles, hub caps, housings for electrical appliances containing small transformers, housings for equipment for the dissemination and transfer of information, housings and cladding for medical purposes, massagers and housings therefor, toy vehicles for children, prefabricated wall panels, housings for safety equipment, rear spoilers, thermally insulated transport containers, facility for holding or caring for small animals, mouldings for sanitary and bath fittings, covering grid plates for ventilation openings, mouldings for summer houses and garden sheds and housings for gardening equipment.
The moulding compositions are particularly suitable for the production of mouldings where particularly high heat resistance is required of the plastics used (e.g. current-carrying components).
Another form of processing is the production of mouldings by thermoforming from previously produced sheets or films.
Thus, the present invention also provides the use of the moulding compositions according to the invention for the production of mouldings of any type, preferably of the types mentioned above, and the mouldings made from the moulding compositions according to the invention.